CN1160291C - Method for production of butanediol - Google Patents
Method for production of butanediol Download PDFInfo
- Publication number
- CN1160291C CN1160291C CNB008061114A CN00806111A CN1160291C CN 1160291 C CN1160291 C CN 1160291C CN B008061114 A CNB008061114 A CN B008061114A CN 00806111 A CN00806111 A CN 00806111A CN 1160291 C CN1160291 C CN 1160291C
- Authority
- CN
- China
- Prior art keywords
- reaction
- butyleneglycol
- vinyl carbinol
- phosphine
- rhodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Health & Medical Sciences (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- General Engineering & Computer Science (AREA)
- Mycology (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Allyl alcohol is hydroformated to 1,4-butanediol using a rhodium and trialkyl phosphine catalyst having at least 2 methyl groups, the reaction first being carried out at milder conditions and subsequently at more, severe conditions.
Description
Background of invention
The invention provides, under different stringent conditions, prepare the method for butyleneglycol by hydroformylation from vinyl carbinol.Preferably in entire method, use identical CO/H
2Reaction mixture gas.
Invention field
The production method for preparing butyleneglycol from vinyl carbinol is known and is business method.Referring to for example United States Patent (USP) 4238419,4678857,4215077,5290743 etc.In general, use rhodium-phosphine catalyst system to make vinyl carbinol and CO/H
2The gas mixture reaction forms the 4-acetaldol, and water extracting and separating from catalyzer goes out the 4-acetaldol and hydrogenation formation butyleneglycol on nickel catalyzator.Referring to United States Patent (USP) 5504261.
Above reaction process relates to different catalyzer and the common different reaction mixture gas of use in each reaction.Obviously, only to use the single catalyst system and preferably only use a kind of reaction mixture gas be useful to the method for preparing butyleneglycol from vinyl carbinol.
Tool report, for example Kawahito etc. uses rhodium and trialkyl phosphine catalyst system can produce butyleneglycol from vinyl carbinol by the single step reaction system in the open No.S52-78809 of Japanese Patent.But the shortcoming of S52-78809 method is 1 of production, and the 4-butyleneglycol is with respect to the 2-methyl isophthalic acid, and the ratio of ammediol is relatively low.
Summary of the invention
The invention provides a kind of use single catalyst system and preferably use single reaction mixture gas to make vinyl carbinol and CO/H
2The method of butyleneglycol is produced in reaction.Beginning is reflected under the gentle relatively condition of temperature and/or pressure and carries out, and this helps to form the straight chain reaction product, the catalyst system rhodium-containing compound of use and aliphatic phosphine.Then, reaction continues to react under same catalyst system and preferred same reaction mixture gas, mainly under stricter reaction conditions forms 1, the 4-butyleneglycol.By practice of the present invention, use two kinds of different catalyzer in the prior art and in reaction process the shortcoming of isolation of intermediate products avoided, and 1, the 4-butyleneglycol is with respect to the 2-methyl isophthalic acid, the ratio of ammediol significantly improves.
Another characteristics, the new catalyst system of the alkylphosphines of use rhodium-containing and following formula makes vinyl carbinol and CO/H
2New reaction takes place.
Wherein R, R
1And R
2In at least two be methyl.R, R
1Or R
2Not that methyl can be C
2-C
20Alkyl or C
3-C
20Cycloalkyl.Be surprisingly found out that, use these phosphines can improve the ratio of linear product and branched product significantly.
Detailed Description Of The Invention
By the present invention, in the presence of rhodium-trialkyl phosphine catalyst system, at first vinyl carbinol and CO/H under gentle relatively condition
2Reaction, this condition helps to form the straight chain reaction product especially.It is 30-100psig with reaction pressure that temperature of reaction is 60-80 ℃; CO/H
2The ratio of mixture is 1/1 mole, but also appropriate change, and can use CO/H
2Dividing potential drop be 5-30psi.Be reflected at and proceed to vinyl carbinol overwhelming majority reaction under these mild conditionss, 60-90% for example, product is mainly the 4-acetaldol, some butyleneglycols and branched chain reaction product.Reaction times under these mild conditionss is generally 1-4 hour.
To be reflected at then under the stricter temperature and pressure condition, for example temperature is that 80-140 ℃ and/or total pressure are that 100-1000psig proceeds in identical catalyzer.Can use identical CO/H
2Gaseous mixture.React under stricter condition, the product of generation is a butyleneglycol, and a high proportion of straight chain and branched product are constant substantially.Usually the suitable reaction times under stringent condition more is 1-10 hour.
In embodiments of the invention, vinyl carbinol and catalyzer preferably place reactor with the solvent that is fit to, and lead to CO/H in reactor
2Reaction gas mixture.In the required reaction times, reactor is heated to temperature of reaction and with CO/H
2The mixture pressurization forms 4-hydroxyl butanols with highly selective.Preferably under agitation carry out.
After this, the temperature of reaction mixture and CO/H
2Pressure increases to stricter condition to form butyleneglycol and these conditions are retained to the required butyleneglycol transformation efficiency of acquisition.
Product mixtures can be separated by diol product being extracted in the water or by vacuum distilling glycol from reaction mixture.
Key character of the present invention is by at first reacting under gentle relatively condition, then more to react under the stringent condition, entire reaction optionally obtains 1, the 4-butyleneglycol, and it is as the advantage product, further significantly reduced branched diol 2-methyl isophthalic acid, the generation of ammediol.In fact, be 3/1 and more a high proportion of straight diol/branched diol by practice of the present invention acquisition ratio easily.
Use and be catalyst system (wherein two alkyl are that methyl and the 3rd are C derived from rhodium or rhodium compound and trialkyl phosphine compound
2-C
12Alkyl).Wherein said rhodium compound is the rhodium carbonyl compound preferably.
Use carbon monoxide and hydrogen mixture, the mol ratio that hydrogen/carbon monoxide is general is 1: 3-10: 1, preferred 1: 2-2: 1 and most preferably 1: 1.Have no adverse effect though change the composition of gas, it is particularly advantageous using identical gaseous mixture in entire reaction course.
Method of the present invention form, continuous or semi-continuous mode is in batches carried out; Preferred continuous mode.
Vinyl carbinol of the present invention and CO/H
2Reaction between reaction gas mixture is basic under gentle relatively condition at first, and this helps to form the hydroxy aldehyde of straight chain.Temperature of reaction is 20-80 ℃, preferred 60-80 ℃, and the total pressure 30-100psig (CO/H of 5-30psig
2Dividing potential drop, 1/1 mol ratio) and first step of reaction be 1-4 hour.
After this, temperature of reaction increases to 80-140 ℃ and pressure to 100-1000psig, is reflected under these stricter conditions and continues 2-4 hour.Use same catalyzer and the same CO/H of preferred use two stages
2Reaction gas mixture.
Reaction mixture has 1 of at least 3/1 ratio, the 4-butyleneglycol: 2-methyl alcohol-1, and ammediol, and these products can separate from catalyzer easily by the method for extraction or vacuum distilling.
Use dimethyl phosphine by the inventive method, use different stringent conditions as stated above and use single reaction conditions all can obtain improved straight chain and branched product ratio.The phosphine that the inventive method is used is trimethyl-phosphine and R, R
1And R
2In two be that methyl and another are C
2-C
12The phosphine compound of alkyl (as dimethyl, the octyl group phosphine).
The present invention can illustrate by following examples.
Embodiment 1
With vinyl carbinol (2g, 34mmol), toluene (30g) and contain dicarbapentaborane acetylacetonate rhodium (0.04g, 0.16mmol) and dimethyl dodecyl phosphine (0.36g, 1.6mmol) catalyzer is put one and is equipped with in the stainless steel pressure container of magnetic stirring apparatus.With this container with gas mixture (CO/H
2=1/1) purge is forced into 100psig with gas mixture, and is heated to 75 ℃.Reacted with this understanding 4 hours, 75% vinyl carbinol reaction this moment, and selectivity generates following product: 67%4-acetaldol, 2.6% hydroxymethyl propionic aldehyde, 11.8%1,4-butyleneglycol and 8.3%2-methyl isophthalic acid, ammediol.
Temperature of reaction is risen to 140 ℃ then, reaction pressure rises to 400psig, and reaction is proceeded 2 hours.The transformation efficiency of the vinyl carbinol when reaction finished in 2 hours is 100% and obtains following productive rate: 74%1, and 4-butyleneglycol and 13%2-methyl isophthalic acid, ammediol.Obtain 11% isopropylcarbinol.
Embodiment 2 (comparison)
Under 100 ℃ and 200psig, repeat the reaction 2 hours of embodiment 1 with similar mixture.Reaction end at 2 hours, the transformation efficiency of vinyl carbinol is 100% and obtains the reaction mixture of following productive rate: 62%4-acetaldol, 3% methylol propionic aldehyde, 6%1,4-butyleneglycol, 8%2-methyl isophthalic acid, ammediol, 16% isobutyric aldehyde and 2% isopropylcarbinol.
These two embodiment have shown the benefit that the fs carries out under mild conditions, can make the ratio of straight chain and side chain improve and reduce C
4By product.
Embodiment 3
In order to show that other dimethyl alkylphosphines also can be used for this single step reaction, use contains dicarbapentaborane acetylacetonate rhodium, and (0.04g, 0.16mmol) (0.23g, catalyzer 1.6mmol) repeats embodiment 1 with dimethyl n hexyl phosphine.After 4 hours, 82% vinyl carbinol reacts in 80 ℃ and 100psig reaction, and selectivity generates following product: 65%4-acetaldol, 2% hydroxymethyl propionic aldehyde, 13%1,4-butyleneglycol and 9%2-methyl isophthalic acid, ammediol.
Temperature of reaction is risen to 140 ℃ then, reaction pressure rises to 400psig, and reaction is proceeded 2 hours.The transformation efficiency of the vinyl carbinol when reaction finished in 2 hours is 100% and obtains following productive rate: 72%1, and 4-butyleneglycol and 12%2-methyl isophthalic acid, ammediol.
Embodiment 4 (comparison)
This two elementary reaction uses triethyl phosphine to carry out as ligand.This kind phosphine ligand was reported in the literature.With vinyl carbinol (2g, 34mmol), toluene (30g) and contain dicarbapentaborane acetylacetonate rhodium (0.04g, 0.16mmol) and triethyl phosphine (0.18g, 1.6mmol) catalyzer is put one and is equipped with in the stainless steel pressure container of magnetic stirring apparatus.This container with the gas mixture purge, is forced into 100psig with gas mixture, and is heated to 70 ℃.Reacted with this understanding 2 hours, 78% vinyl carbinol reaction this moment, and the reaction of catalyst system vinyl carbinol, and selectivity generates following product: 55%4-acetaldol, 37% hydroxymethyl propionic aldehyde, 2%1,4-butyleneglycol and 3%2-methyl isophthalic acid, ammediol.
Temperature of reaction is risen to 120 ℃ then, reaction pressure rises to 400psig, and reaction is proceeded 2 hours.The transformation efficiency of the vinyl carbinol when reaction finished in 2 hours is 100%.Obtain 57%1,4-butyleneglycol and 39%2-methyl isophthalic acid, ammediol.
Embodiment 5 (comparison)
The outer another kind of trialkyl phosphine of triethyl phosphine is used for this two elementary reaction.Use contain dicarbapentaborane acetylacetonate rhodium (0.04g, 0.16mmol) and tri-n-butyl phosphine (0.33g, embodiment above 1.6mmol) catalyzer repeats.In 70 ℃ and 100psig reaction after 3 hours, the reaction of 75% vinyl carbinol, and selectivity generates following product: 52%4-acetaldol, 33% hydroxymethyl propionic aldehyde, 5%1,4-butyleneglycol and 7%2-methyl isophthalic acid, ammediol.
Temperature of reaction is risen to 140 ℃ then, reaction pressure rises to 400psig, and reaction is proceeded 2 hours.The transformation efficiency of the vinyl carbinol when reaction finished in 2 hours is 100%, obtains 56%1,4-butyleneglycol and 37%2-methyl isophthalic acid, ammediol.
When attention can not make reaction finish, need to increase the reaction times under the mild conditions of fs.
Claims (8)
1. a trialkyl phosphine catalyzer that uses rhodium-containing or rhodium compound and at least two methyl is by vinyl carbinol and CO/H
2The carbonylation of gas mixture prepares 1, and the method for 4-butyleneglycol, this method comprise a) under 20-80 ℃ and 308-791kPa carries out the vinyl carbinol reaction of carbonylation at least 50% weight; And b) continues that reaction forms 1, the 4-butyleneglycol under the stricter condition of 80-140 ℃ and 791-6996kPa.
2. the process of claim 1 wherein that said phosphine comprises trimethyl-phosphine.
3. the process of claim 1 wherein said phosphine as shown in the formula:
R(CH
3)
2P
Wherein R represents C
2-C
20Alkyl or C
3-C
20Cycloalkyl.
4. the method for above arbitrary claim wherein a) proceeds to the vinyl carbinol reaction of 60-90%.
5. the method for above arbitrary claim wherein a) proceeds to the vinyl carbinol reaction of 60-90% under 60-80 ℃ and 308-791kPa.
6. the method for above arbitrary claim is wherein used identical CO/H in step a) and step b)
2Gaseous mixture.
7. the method for above arbitrary claim, wherein H
2: the mol ratio of CO is 1: 3 to 10: 1.
8. the method for above arbitrary claim, wherein rhodium compound is the rhodium carbonyl compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/291,737 US6127584A (en) | 1999-04-14 | 1999-04-14 | Butanediol production |
| US09/291,737 | 1999-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1346340A CN1346340A (en) | 2002-04-24 |
| CN1160291C true CN1160291C (en) | 2004-08-04 |
Family
ID=23121620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008061114A Expired - Fee Related CN1160291C (en) | 1999-04-14 | 2000-03-29 | Method for production of butanediol |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6127584A (en) |
| EP (1) | EP1171407B1 (en) |
| JP (1) | JP2002542211A (en) |
| KR (1) | KR20010112939A (en) |
| CN (1) | CN1160291C (en) |
| AT (1) | ATE258542T1 (en) |
| AU (1) | AU4112800A (en) |
| BR (1) | BR0009735A (en) |
| CA (1) | CA2365332A1 (en) |
| DE (1) | DE60007975D1 (en) |
| MX (1) | MXPA01010338A (en) |
| RU (1) | RU2001127847A (en) |
| WO (1) | WO2000063143A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426437B1 (en) * | 2000-12-13 | 2002-07-30 | Arco Chemical Technology, L.P. | Hydroformylation process |
| EP1651587A1 (en) * | 2003-07-03 | 2006-05-03 | Lucite International UK Limited | Process for the hydroformylation of ethylenically unsaturated compounds |
| US7271295B1 (en) * | 2006-10-13 | 2007-09-18 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
| US7279606B1 (en) | 2007-04-02 | 2007-10-09 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
| US7655821B1 (en) | 2008-11-25 | 2010-02-02 | Lyondell Chemical Technology, L.P. | Direct hydrocarbonylation process |
| US7790932B1 (en) | 2009-12-21 | 2010-09-07 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
| TWI395729B (en) * | 2011-01-14 | 2013-05-11 | China Petrochemical Dev Corp | A method for producing a dihydric alcohol compound |
| TWI586643B (en) * | 2012-05-29 | 2017-06-11 | 利安德化學科技有限公司 | Rate and selectivity improvement in hydroformylation of allyl alcohol |
| FR2993557B1 (en) | 2012-07-23 | 2015-11-13 | Arkema France | SYNTHESIS OF METHYL PROPANE DIOL FROM ALLYL ALCOHOL |
| US8742180B1 (en) | 2012-11-13 | 2014-06-03 | Lyondell Chemical Technology, L.P. | Process control with Raman spectroscopy |
| CN105308011A (en) * | 2013-07-02 | 2016-02-03 | 三菱化学株式会社 | 1,4-butanediol, method for producing polyester using said 1,4-butanediol, and storage method for said 1,4-butanediol |
| CA2922120C (en) | 2013-09-03 | 2022-09-06 | Myriant Corporation | A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
| US9765005B2 (en) * | 2014-09-09 | 2017-09-19 | Lyondell Chemical Technology, L.P. | Methods of using homogenous rhodium catalysts with N-heterocyclic carbene ligands for the hydroformylation of olefins and substituted olefins |
| US9950981B2 (en) | 2014-09-09 | 2018-04-24 | Lyondell Chemical Technology, L.P. | Allyl alcohol hydroformylation process |
| EP3181546B1 (en) | 2015-12-16 | 2018-05-02 | Evonik Degussa GmbH | Method of double carbonylation of allylic alcohols in order to form corresponding diesters |
| CN112457165A (en) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | Reinforcing system and process for preparing 1, 4-butanediol by allyl alcohol hydrogenation |
| CN115433065B (en) * | 2022-08-22 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method of 1, 3-butanediol |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4064145A (en) * | 1975-10-20 | 1977-12-20 | Celanese Corporation | Production of tetrahydrofuran |
| JPS5278809A (en) * | 1975-12-26 | 1977-07-02 | Ube Ind Ltd | Preparation of 1, 4-butanediol |
| GB1565719A (en) * | 1976-12-30 | 1980-04-23 | Gen Electric | Process for preparing butanediols |
| US4215077A (en) * | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
| FR2428021A1 (en) * | 1978-06-05 | 1980-01-04 | Kuraray Co | HYDROFORMYLATION OF OLEFINIC COMPOUNDS |
| US4590311A (en) * | 1983-12-29 | 1986-05-20 | Shell Oil Company | Process for the preparation of 1,4-butanediol |
| US4678857A (en) * | 1986-03-31 | 1987-07-07 | Texaco Inc. | Process for separation of product resulting from hydroformylation |
| JPH03109338A (en) * | 1989-09-22 | 1991-05-09 | Agency Of Ind Science & Technol | Production of alcohol using hydrocarbon as raw material |
| GB8921947D0 (en) * | 1989-09-28 | 1989-11-15 | British Petroleum Co Plc | Process for the formation of alcohols |
| US5290743A (en) * | 1993-03-22 | 1994-03-01 | Arco Chemical Technology L.P. | Process for regenerating a deactivated rhodium hydroformylation catalyst system |
| US5504261A (en) * | 1994-08-01 | 1996-04-02 | Arco Chemical Technology, L.P. | Production of hydroxy compounds |
-
1999
- 1999-04-14 US US09/291,737 patent/US6127584A/en not_active Expired - Fee Related
-
2000
- 2000-03-29 CA CA002365332A patent/CA2365332A1/en not_active Abandoned
- 2000-03-29 KR KR1020017012993A patent/KR20010112939A/en not_active Application Discontinuation
- 2000-03-29 AT AT00920611T patent/ATE258542T1/en not_active IP Right Cessation
- 2000-03-29 JP JP2000612240A patent/JP2002542211A/en active Pending
- 2000-03-29 MX MXPA01010338A patent/MXPA01010338A/en not_active Application Discontinuation
- 2000-03-29 CN CNB008061114A patent/CN1160291C/en not_active Expired - Fee Related
- 2000-03-29 DE DE60007975T patent/DE60007975D1/en not_active Expired - Lifetime
- 2000-03-29 AU AU41128/00A patent/AU4112800A/en not_active Abandoned
- 2000-03-29 WO PCT/EP2000/002743 patent/WO2000063143A1/en not_active Application Discontinuation
- 2000-03-29 BR BR0009735-7A patent/BR0009735A/en not_active Application Discontinuation
- 2000-03-29 EP EP00920611A patent/EP1171407B1/en not_active Expired - Lifetime
- 2000-03-29 RU RU2001127847/04A patent/RU2001127847A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU4112800A (en) | 2000-11-02 |
| BR0009735A (en) | 2002-01-02 |
| JP2002542211A (en) | 2002-12-10 |
| US6127584A (en) | 2000-10-03 |
| MXPA01010338A (en) | 2002-05-06 |
| WO2000063143A1 (en) | 2000-10-26 |
| CA2365332A1 (en) | 2000-10-26 |
| RU2001127847A (en) | 2004-02-20 |
| EP1171407A1 (en) | 2002-01-16 |
| CN1346340A (en) | 2002-04-24 |
| KR20010112939A (en) | 2001-12-22 |
| EP1171407B1 (en) | 2004-01-28 |
| ATE258542T1 (en) | 2004-02-15 |
| DE60007975D1 (en) | 2004-03-04 |
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